This is much more complicated than it seems. Keep in mind, the Universe keeps expanding, so even as one photon leaves the galaxy on its way towards us, that galaxy has already moved a bit further away.
So, as you measure the red shift and whatnot, all you could say is "these particular photons have traveled 10 Gly to reach us", but you can't say "the distance right now from here to that galaxy is 10 Gly". That galaxy is already further away by now.
To complicate things even more, this is a relativistic universe, so the word "now" does not have a unique, generally-agreed-upon meaning for all observers. Your "now" is different from my "now", which is different from the "now" of someone living in the Andromeda galaxy. This is not because we don't measure time precisely enough, but it's an inherent attribute of time in a relativistic universe. Relativistic space-time is not this crystal clear background we're moving through, but it's more like molasses or a rubber sheet, it flows and bends depending on what you do or where you are.
To answer your question specifically, all you could say is "the image of this galaxy, from my perspective 'now', is at 10 Gly; the image of that other galaxy, from my perspective 'now', is at 10 Gly in the opposite direction; so these images, seen from my particular point in space and time, are as if they are separated by 20 Gly".
You could calculate where those galaxies are "now", from your perspective, and you may even deduce that they are at 12 Gly each, so therefore they are separated "now" by 24 Gly. But, again, another observer, in a different place in space-time or phase-space, may obtain a different result - and both results, yours and theirs, are equally correct. The difference will likely be very small, unless extremely high velocities or energies are involved, but be aware that it exists.
EDIT: I assumed a more or less flat space-time in all of the above. If that assumption is not correct, then that's another source of fuzziness for the results.